Resinous composition and method for producing the same



Patented Oct. 15, 1946 OFFICE 2,409,332 nesmous COMPOSITION AND METHODFOR PRODUCING THE SAME Howard 0. Woodruff, Philadelphia, Pa.

No Drawing. Application May 29, 1942, Serial No. 444,999

3 Claims.

The coating and resinous compositions of my present invention are highlycomplex materials having improved compatibility, improved hardness, andimproved stability and the technical operations in which they areemployed are greatly simplified.

It is an object of my invention to produce complex varnish resins whichare readily soluble in highly polymerized drying oils. It is also anobject of my invention to produce oil compositions which easily dissolvehighly polymeric resins. It is further an object of my invention to'process diflicultly-oil-soluble varnish resins, to render them easilysoluble without interfering with their otherwise technically desirablecharacteristics.

It is further an object of my invention to produce new compositions ofmatter useful as Varnish resins, lacquer resins, and as a basis for newcoating compositions.

Highly complex varnish resins can be dissolved in highly polymerizedvarnish oils only at exthe ingredients increasing as the individualelement-complexity increases.

This invention has as an object the decreasing of a large measure ofthese difficulties.

These objects are accomplished by treating polyglyceride esters, orother condensed polyhydric or polymerized polyhydric alcohol esters Withpolyhydric alcohols and the subsequent production of diethers and theuse of these ether-bearing materials with other chemicals to produce theproperties desired. i

For purposes of discussion polyglyceride esters are here discussed butthis is not to be construed as a limitation, since the esters of othercondensed or polymerized polyhydric alcohols undergo the same or similaror analogous reactions.

Polyglyceride esters are compounds conforming to the general formula inwhich R represents any acid group. Usually however R represents acomplex organic acid, a fatty oil acid, a resinous acid, or a complexresinous acid, or a modified fatty oil acid. In the formula N representsany small whole number of the groups within theruling.

Polyglyceride esters may be prepared by the following methods:

By direct esterification of polyglycerolas outlined by E. M. Symmes, U.S. Patent No.;1,696,337. By elimination-of water between two mols ofdiglyceride esters as described by T. F. Bradley, Industrial andEngineering Chemistry 28, 5, 579 (1937). a o

By reacting acids with glycerine in excess of that required to formtriglycerides as described by H. C. W oodruihPaint and VarnishProduction taining compounds or compositions which con- The ether thusformed is highly reactive and its oxygen unites with two hydroxyls of apolyalcohol such as pentaerythritol H? ()H H2O CH1 HO CC(|JOH To formtwo ether groups and Water HiCOOCR RCOOCH: H20

H230 CR RC 0 OCH HzC-O O-GH:

H20 CH2 0 C It. s.

OH OH The remaining hydroxyls react with many acids such as resin andothers named above.

Throughout the process and in the final composition the pentaerythritolnucleus consisting of a central carbon atom, to whichfour CH2 groups areattached, remains unchanged in its tertiary carbon characters.

The propyl group of glycerine, the

retains its identity throughout its reactions.

In the case of the Simple glycols reacting with polyglyceride esters nofurther treatment is necessary to obtain the desired results. Howeverthe reaction products between polyglycerol esters and polydialcoholsand/or dipolyalcohols conduct themselves exactly similar to polyglycerolesters, but with certain desirable and advantageous properties.

The reaction between an acid and a polyhyclric composition produced bythe action of a polyhydric alcohol on a reaction product of apolydialcohol or a dipolyalcohol and a polyglycerol ester also comeswithin the scope of this invention.

The reactions are conducted at temperatures usually less than 600 F. inan open or closed reaction kettle and preferably, although notnecessarily under vacuum. The mass may or may 4 not be agitated,although agitation is considerably helpful.

The follOWing examples are for the purpose of illustration only and arenot to be so construed as to limit the invention as to proportions orscope. Parts are by weight. Melting points are taken by the mercurymethod.

EXAMPLE 1 A22 resin Parts WW wood rosin 1,000 Glycerine 135 Under airreflux held 550 F. until clear in toluol and an additional hour.

A. N. 2.8, Zerewitinoff hydroxyl hydrogen corrected .02%, alcoholtitration 25.0, M. P. (Hg) 77 C; Ether content (acid absorption method)55%, water extractable glycerine 0.25%.

Alcohol titration test is a measure of lacquer compatibility. 10 gr. ofresin are dissolved in 10 gr. of toluol. The alcohol titration is the c.c. of alcohol required to cloud the solution.

Acid absorption method consists of heating resin with excess rosin at530F. until the acid number is constant. The rosin absorbed is thencalculated to per cent polyglyceride ester (or ether) in the resintaken. Corrections are made for free hydroxyl groups which arepreviously determined by the Zerewitinoff method corrected for acidvalue.

Parts A22 resin 120 Mannitol 5 Completely dissolved at 570 F. after 5minutes, added maleic anhydride 5 parts. Held 530 F. 5 hrs. A. N. 14, M.P. 240 F.

Varnish prepared from this resin:

Parts Resin Linseed oil previously heated at 580 F. to a cold string 200Cobalt naphthenate: .05% cobalt metal on weight of oil.

Resin dissolved clear in stringed oil at 530 F. Viscosity 50%, solids inmineral spirits: D-E. Excellent drying and water resistancecharacteristics.

Pentaerythritol can be substituted for mannitol with equivalent results.

EXAMPLE 2 Parts A22 resin Mannitol 5 EXAMPLE 3 Parts Resin A22 500Di-ethylene glycol 25 Refiuxed at 540 F. 6 hrs. Zerewitinoff hydroxylhydrogen content 0.01%, ether content (acid absorption method) 69%, A.N. 3.2, alcohol titration 34.2, M. P. 60 C. Added glycerine 40 parts,refluxed at 540 F. 3% hrs. Water extractable glycerine 0.4%; added 5maleic anhydride 27 parts; held 520-530 F. 3 hrs. A. N. 7.3. M. P. 250F.

Varnish Parts Resin p 100 Linseed oil heated to a cold string 200 Cobaltnaphthenate: 0.05% cobalt metal on weight of oil.

300 parts mineral thinner. Resin dissolved clear. Viscosity F-G. Dryingand Water resistance slightly better than resin of Example No, 1 in sameformula.

EXAMPLE 4 Parts A22 resin 120 Mannitol Completely dissolved at 570 F. inminutes; added maleic anhydride 5 parts. Held 530 F. 5% hrs. A. N. 16.3,alcohol titration 23.0, M. P. 227 F.

Varnish Viscosity C-D.

. Parts Mineral thinner 300 Resin containing maleic anhydride 100Linseed oil heated to a cold string 200 Cobalt naphthenate: .05% cobalton weight of oil. Resin dissolved clear in stringed oil at 530 F.Surface dry equals Example No. 3 but not quite so good thru dry. Verslightly less water resistance.

In this example pentaerythritol may be used interchangeably withmannitol.

Lacquer Parts Resin containing maleic anhydride 100 Blown castor oil 100Nitrocellulose 100 Lacquer thinner; 300

A clear nonblushing lacquer was produced, of remarkable plasticity andadhesion,

EXAMPLE 5 Resin PhA Parts Diphenylolpropanenun 100 Formaldehyde, 36% aq220 Combined by reacting in aq. alkali medium at 60 C. for 48 hrs. Freedfrom alkali by carefully neutralizing with HCl and washing with WarmH20.

Added this resin dissolved in an equal weight of alcohol to WW woodrosin 700 parts, while maintaining temperature at 400 F., a terpenicphenolic modified acid is thus produced.

Parts A22 resin (ref. Example No. 1) 1,000 Mannitol n 80 l Dissolvedmannitol in 15 minutes at 570 F. added resin PhA 800 parts. Heldtemperature at 530 F. 4 hrs. A. N. 15.3, viscosity 50% in toluol B-C, M.P. 270 F.

. Parts 1 Mineral thinner -1 300 Resin 100 Linseed oil heated to'a coldstring 200 Cobalt naphthenate:

weight of oil.

Resin dissolved clear in stringed oil at520-525 F, Viscosity 50% mineralspirits F-G.

05% cobalt metal on 6 Drying exceptionallyhard fast drying varnish.Pentaerythritol may be substituted for mannitol in this example.

EXAMPLE 6 C3? resin Parts 1. Soya oil 776 2. LB dehydrated castor oil259 3. Glycerine 240 4. Phthalicanhydri'de 725 5.. Fumaric acid 15 6.Glycerine I, 2, 3 heated at 510 F. under reflux until soluble in 2 vols.of methanol; 4 and 5 added, temperature held 420-430 F. to A. N. lessthan 10.

Characteristics A. N. solids 8.0.

C37A.50% solution in mineral spirits.

viscosity Z3.

Equalparts oil and alkyd solution. Will not blend clear with linseed oilbodied to Z viscosity.

C37B.-Thinned to viscosity H with mineral spir- .its, added lead andcobalt naphthenate to equal 0.3% lead and 0.05% cobalt as metal based onthe weight of the solids.

Drying-Set 2 hrs. Tack free 6-7 hrs. in cold H20 24 hrs. Recovers in 1hrs.

This is a commercial standard type alkyd used for reference.

Color 6,

White 7 Parts Resin. C37 solids 300 Ethylene glycol 10 Refluxed 2 hrs.at 475 F.; raised temperature to 530 F., held 2 hrs. Alkyd was thenclear in toluol solution, the diglyceride ethers in the Resin C37solidshaving reacted with the two hydroxyls of the glycol with theelimination of water produce a more blendable alkyd due to the ether(ROCH2CH2-O-R) bond between the large molecular segments of the originalalkyd andthemore widely separated stearic condition thus produced.

Characteristics Characteristics A. N. solids 5.2. 50% solution inmineral thinner. Color 6, viscosity Z1-Z2. Clear blend with equal partby weight Z linseed oil.

Thinner and drier same as C37B.

Drying.-Set 2 hrs. Tack free 6-7 hrs. White in cold H2O after 24 hrs.Recovers after 1% hrs.

This alkyd has exceptional blending characteristics with ureaformaldehyde resin solutions, andwith a wide variety of oleoresinousvarnishes.

7 EXAMPLE '7 Parts Resin solids from Example No. 6 1,000 Glycerine 30Heated at 560 F. under reflux for 3 hrs., solution in toluol was thenclear. Added phthalic anhydride 20 parts. Held 540 F. 2 hrs.

Characteristics A. N. solids 7.0. 50% solution in mineral spirits. Color6. Viscosity Z5-Z6. Blends clear with an equal weight of Z linseed oil.Thinner and driers same as 037B.

Drying.Set 2 hrs. Tack free 5-5 hrs. Very slightly white in cold H2Oafter 24 hrs. Recovers in less than 1 hr. 7

In spite of the greatly increased viscosity this resin retains the sameblendability as the resin in Example 6. An equivalent weight oftrimethylol propane can be substituted for glycerine.

EXAMPLE 8 Parts Varnish makers alkali refined linseed oil 1,000Glycerine 6 Reflux at 540 F. 4 hrs. Raise temperature to 580 F, hold 5hrs. Apply vacuum at 580 F. for 1 hrs. Zerewitinoff hydroxyl hydrogen0.04%, ether content by acid absorption method 31%. Water extractableglycerine, none detectable. Add ethylene glycol 40 parts. Refluxed 450F. 3 hrs. Raised to 540 F., held 2 hrs. Viscosity Y-Z.

Extractable ethylene glycol 0.3%, Zerewitinofi hydroxyl hydrogen 0.04%.

Analysis show this to be the di-ether of ethylene glycol in which thetwo carbons of the glycol are-attached to alpha carbon atoms of twodiglyceride esters by ether oxygen linkages.

The oil product thus obtained is much more compatible with resins thanuntreated Z linseed oil. The glycol treatment does not interfere withdrying or resistance characteristics.

Z linseed oil will not form a clear mix with C3'7A resin.

The oil produced in this example produces a perfectly clear mixturewhich remains clear and compatible when flowed on glass.

EXAMPLE 9 Resin D71 Parts Maleic anhydride 100 Glycerine 140 WW gumrosin -2 850 Reflux maleic anhydride with glycerine at 420 'F. for hr.;add to the gum rosin at 350-375 F.;

- Cobalt naphthenate drier: 0.05% cobalt on Weight of oil.

Oil and resin heated to 570 F., held 590 F. 10 min., cooled to 450 F.,thinned and drier added.

A -Z.l i nseed oil dissolved the resin only after 1 8 minute at 590 F.The oil prepared in Example No. 8 dissolved the resin clear at 450 F.

The varnish prepared from Z linseed oil had a viscosity of G and wouldnot blend with alkyd resin C37 (Example 6) in equal parts by weight.

The varnish prepared from the oil produced in Example No. 8 had aviscosity of F and blended clear in all proportions with alkyd resin C37(Example No.6).

The water resistance of the dried films was identical.

Both varnishes were made into gloss white enamels by grinding withtitanium dioxide pigment in the ratio of three pounds of pigment pergallon of vehicle. Both enamels had identical drying characteristics.The enamel based on the oil produced in Example No. 8 had considerablybetter brushing characteristics. After- 10 months exposure the enamelbased on the oil produced in Experiment No. 8 was much better for glosretention than the enamel based on Z linseed oil.

EXAMPLE 10 Resin D71 B Resin PhA (Example No. 5) is heated to 530 F.with gr. of glycerine and held at this temperature 6 hrs. A high meltinghigh viscosity modified phenolic resin is thus produced.

A. N. 12-14, viscosity 50%, solution in toluol D-E, M. P. 150-155 C.Zerewitinoff hydroxyl hydrogen (corrected) 0.06%.

When used in varnish formula of Example No. 9 it will be found todissolve in the oil produced in Example No. 8 at 500 F. or less, whileordinary Z linseed oil will not dissolve the resin at lower than 590 F.

The use of the oil produced in Example No. 8 greatly improves thestability of this type of varnish. This stability can be shown onaerating the respective varnishes. The varnishes are placed in glassutensils and air passed through. The rate of flow is adjusted to beidentical for both varnishes. It is found that the varnish based on theZ linseed oil will seed and jell in 2-4 hours depending on the rate offlow while the varnish based on theoil produced in Example 8 will notjell on greatly prolonged treatment with EXAMPLE 11 Resin E94 PartsResin D71B (Example No. 10) 500 Ethylene glycol; 15

lowing varm'sh preparation:

Varnish Parts Resin Body Z linseed oil 200 Mineral thinner 300 Cobaltnaphthenate: 0.05% cobalt on weight of oil.

Oil and resin heated to 590 F., held 590 F. 10 minutes, cooled to 450F., thinned and added'cobalt naphthenate.

Using this procedure Resin D'IlB will dissolve only after 590 F. isreached, while Resin E94 will dissolve easily to a clear solution at 500F. or less. The resin E94 Varnish will be found stable when tested asabove while the D713 Resin Varnish will not.

Similar varnish characteristics are produced when Resin D71 issubstituted for D713 in this example.

My improved products are useful as ingredients of coating compositionsfor wood, metal, etc. For this purpose they may be used either alone orcombined by mutual solvents, by heating, or by other means, with one ormore of the following: cellulose derivatives such as ethyl cellulose,nitrocellulose, cellulose acetate, benzyl cellulose, celuloseacetopropionate, natural gums such as kauri, rosin, and damar; combinednatural gums such as ester gum, methyl and ethyl abietate; drying oilssuch as linseed, and tung oil; other synthetic resins, such as phenolformaldehyde, amine aldehyde, vinyl and asphalts or bitumens. To myproducts, either alone or combined with the above substances, pigments,fillers, lakes, plasticizers, antioxidants, solvents, etc., may be addedas needed and desired. Any known methods of applying the finish such asspraying, brushing, baking, air drying, etc., may be used.

From the foregoing it will be apparent that I have developed a newmethod for treating oils and resins which offers many advantages. As

compared to known methods of working it allows the production ofmaterials ofa much wider range of blendability, and therefore utility.The resistance is not undesirably afiected and in many cases the dryingis improved. It is also possible to produce stable varnishes with easeand to increase the viscosity of certain types of resins and at the sametime improve compatibility and blendability.

As many apparently different embodiments of this invention may be madeWithout departing from the spirit and scope thereof, it is to beunderstood that I do not limit myself to the specific embodimentsthereof except as defined in the followingclaims.

I claim:

1. A new composition of matter, a terpenic resinous acid ester ofpentaerythritol-glycerine

